EP3645662B1 - Dérives du 2,3-dihydrobenzothiophène - Google Patents
Dérives du 2,3-dihydrobenzothiophène Download PDFInfo
- Publication number
- EP3645662B1 EP3645662B1 EP18732360.5A EP18732360A EP3645662B1 EP 3645662 B1 EP3645662 B1 EP 3645662B1 EP 18732360 A EP18732360 A EP 18732360A EP 3645662 B1 EP3645662 B1 EP 3645662B1
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- YJUFGFXVASPYFQ-UHFFFAOYSA-N 2,3-dihydro-1-benzothiophene Chemical class C1=CC=C2SCCC2=C1 YJUFGFXVASPYFQ-UHFFFAOYSA-N 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims description 75
- -1 tetrahydrofuran-2,5-diyl Chemical group 0.000 claims description 39
- 229910052731 fluorine Inorganic materials 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 9
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims description 7
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 claims description 3
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 132
- 0 *C(CC1)CCC1C(CC1)CCC1C(C1)Sc2c1cc(*)c(-c1ccc(*)cc1)c2* Chemical compound *C(CC1)CCC1C(CC1)CCC1C(C1)Sc2c1cc(*)c(-c1ccc(*)cc1)c2* 0.000 description 20
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 17
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 17
- 239000004973 liquid crystal related substance Substances 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 8
- GVBXHTCVVDWREE-UHFFFAOYSA-N Cc(ccc(C)n1)c1F Chemical compound Cc(ccc(C)n1)c1F GVBXHTCVVDWREE-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 238000000819 phase cycle Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- DYSJQUQJVBYIOT-UHFFFAOYSA-N Cc(ccc(C)c1F)c1F Chemical compound Cc(ccc(C)c1F)c1F DYSJQUQJVBYIOT-UHFFFAOYSA-N 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000003818 flash chromatography Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- FEWLNYSYJNLUOO-UHFFFAOYSA-N 1-Piperidinecarboxaldehyde Chemical compound O=CN1CCCCC1 FEWLNYSYJNLUOO-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- PJYHAWAWFSRYLF-UHFFFAOYSA-N FC1=C(C=CC=2CC(SC=21)C1CCC(CC1)CCC)OCCCC Chemical compound FC1=C(C=CC=2CC(SC=21)C1CCC(CC1)CCC)OCCCC PJYHAWAWFSRYLF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000008423 fluorobenzenes Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- SJSRFXJWBKOROD-UHFFFAOYSA-N 1,1'-bi(cyclohexyl)-1-carboxylic acid Chemical class C1CCCCC1C1(C(=O)O)CCCCC1 SJSRFXJWBKOROD-UHFFFAOYSA-N 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- IMWYPAPRPMKORW-UHFFFAOYSA-N 4-butoxy-2,3-difluorobenzaldehyde Chemical compound CCCCOC1=CC=C(C=O)C(F)=C1F IMWYPAPRPMKORW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VRFUMZAWQRTPBF-UHFFFAOYSA-N C(CCC)OC1=C(C2=C(C=C(S2)C(=O)O)C=C1)F Chemical compound C(CCC)OC1=C(C2=C(C=C(S2)C(=O)O)C=C1)F VRFUMZAWQRTPBF-UHFFFAOYSA-N 0.000 description 2
- QDSXDVPRZDXWNU-UHFFFAOYSA-N C(CCC)OC1=C(C2=C(C=C(S2)C2=CCC(CC2)CCC)C=C1)F Chemical compound C(CCC)OC1=C(C2=C(C=C(S2)C2=CCC(CC2)CCC)C=C1)F QDSXDVPRZDXWNU-UHFFFAOYSA-N 0.000 description 2
- JXHWARQXTPFZQY-UHFFFAOYSA-N C(CCC)OC1=C(C2=C(C=CS2)C=C1)F Chemical compound C(CCC)OC1=C(C2=C(C=CS2)C=C1)F JXHWARQXTPFZQY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- MKIJJIMOAABWGF-UHFFFAOYSA-N methyl 2-sulfanylacetate Chemical compound COC(=O)CS MKIJJIMOAABWGF-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- IWIOHRVOBOYWQE-UHFFFAOYSA-N (1-cyclohexylcyclohexyl)benzene Chemical class C1CCCCC1C1(C=2C=CC=CC=2)CCCCC1 IWIOHRVOBOYWQE-UHFFFAOYSA-N 0.000 description 1
- JYNLTWJPPFIEFR-UHFFFAOYSA-N 1,2-dicyclohexylcyclohexene Chemical class C1CCCCC1C1=C(C2CCCCC2)CCCC1 JYNLTWJPPFIEFR-UHFFFAOYSA-N 0.000 description 1
- 150000005481 1,2-diphenylethanes Chemical class 0.000 description 1
- UPJKDKOHHMKJAY-UHFFFAOYSA-M 1,3-dicyclohexylimidazol-1-ium;chloride Chemical compound [Cl-].C1CCCCC1N1C=[N+](C2CCCCC2)C=C1 UPJKDKOHHMKJAY-UHFFFAOYSA-M 0.000 description 1
- QQFSIGWYINAJOB-UHFFFAOYSA-N 1,4-dicyclohexylbenzene Chemical class C1CCCCC1C1=CC=C(C2CCCCC2)C=C1 QQFSIGWYINAJOB-UHFFFAOYSA-N 0.000 description 1
- DIHPKCMKWXFURJ-UHFFFAOYSA-N 1-(2-cyclohexylethyl)-2-phenylbenzene Chemical class C1CCCCC1CCC1=CC=CC=C1C1=CC=CC=C1 DIHPKCMKWXFURJ-UHFFFAOYSA-N 0.000 description 1
- DYSJMQABFPKAQM-UHFFFAOYSA-N 1-benzothiophene-2-carboxylic acid Chemical class C1=CC=C2SC(C(=O)O)=CC2=C1 DYSJMQABFPKAQM-UHFFFAOYSA-N 0.000 description 1
- HYDIPEHDSUNHPA-UHFFFAOYSA-N 1-butoxy-2,3-difluorobenzene Chemical compound CCCCOC1=CC=CC(F)=C1F HYDIPEHDSUNHPA-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- YQSAPDQJFZPHOJ-UHFFFAOYSA-N 2-cyclohexyl-1,3-dithiane Chemical class C1CCCCC1C1SCCCS1 YQSAPDQJFZPHOJ-UHFFFAOYSA-N 0.000 description 1
- SMHSPYVJAUGNOI-UHFFFAOYSA-N 2-cyclohexyl-1,4-dioxane Chemical class C1CCCCC1C1OCCOC1 SMHSPYVJAUGNOI-UHFFFAOYSA-N 0.000 description 1
- ZKTFZNPTAJIXMK-UHFFFAOYSA-N 2-cyclohexylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1CCCCC1 ZKTFZNPTAJIXMK-UHFFFAOYSA-N 0.000 description 1
- HYYFAYFMSHAWFA-UHFFFAOYSA-N 2-cyclohexylethylbenzene Chemical class C1CCCCC1CCC1=CC=CC=C1 HYYFAYFMSHAWFA-UHFFFAOYSA-N 0.000 description 1
- IBLVSWYGUFGDMF-UHFFFAOYSA-N 2-cyclohexylethylcyclohexane Chemical class C1CCCCC1CCC1CCCCC1 IBLVSWYGUFGDMF-UHFFFAOYSA-N 0.000 description 1
- HUTHUTALXJNNRS-UHFFFAOYSA-N 2-cyclohexylpyridine Chemical class C1CCCCC1C1=CC=CC=N1 HUTHUTALXJNNRS-UHFFFAOYSA-N 0.000 description 1
- YJDDXMSIMBMMGY-UHFFFAOYSA-N 2-cyclohexylpyrimidine Chemical class C1CCCCC1C1=NC=CC=N1 YJDDXMSIMBMMGY-UHFFFAOYSA-N 0.000 description 1
- NQEDLIZOPMNZMC-UHFFFAOYSA-N 4-propylcyclohexan-1-one Chemical compound CCCC1CCC(=O)CC1 NQEDLIZOPMNZMC-UHFFFAOYSA-N 0.000 description 1
- QNGKGXNZGWIDGS-UHFFFAOYSA-N 6-cyclohexyl-5-ethyl-5-phenylcyclohexa-1,3-diene Chemical class C=1C=CC=CC=1C1(CC)C=CC=CC1C1CCCCC1 QNGKGXNZGWIDGS-UHFFFAOYSA-N 0.000 description 1
- LWLCGSRLAKYFJE-UHFFFAOYSA-N C(CCC)OC1=C(C2=C(C=C(S2)C(=O)OC)C=C1)F Chemical compound C(CCC)OC1=C(C2=C(C=C(S2)C(=O)OC)C=C1)F LWLCGSRLAKYFJE-UHFFFAOYSA-N 0.000 description 1
- KTCYRQYFAFLPAW-UHFFFAOYSA-N C(CCC)OC1=C(C2=C(C=C(S2)C2CCC(CC2)CCC)C=C1)F Chemical compound C(CCC)OC1=C(C2=C(C=C(S2)C2CCC(CC2)CCC)C=C1)F KTCYRQYFAFLPAW-UHFFFAOYSA-N 0.000 description 1
- LKZODYBLXMPZFZ-UHFFFAOYSA-N CCCCOc(ccc(C1)c2SC1c(c(F)c1F)ccc1OCC)c2F Chemical compound CCCCOc(ccc(C1)c2SC1c(c(F)c1F)ccc1OCC)c2F LKZODYBLXMPZFZ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- ADIAPCNCEHFEPJ-UHFFFAOYSA-N [4-(2-cyclohexylethyl)cyclohexyl]benzene Chemical class C1CCCCC1CCC(CC1)CCC1C1=CC=CC=C1 ADIAPCNCEHFEPJ-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000001482 benzyl phenyl ethers Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid group Chemical class C(C=CC1=CC=CC=C1)(=O)O WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Chemical group 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical class *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- DQZKGSRJOUYVPL-UHFFFAOYSA-N cyclohexyl benzoate Chemical class C=1C=CC=CC=1C(=O)OC1CCCCC1 DQZKGSRJOUYVPL-UHFFFAOYSA-N 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical class C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical class C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- CETRZFQIITUQQL-UHFFFAOYSA-N dmso dimethylsulfoxide Chemical compound CS(C)=O.CS(C)=O CETRZFQIITUQQL-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940052296 esters of benzoic acid for local anesthesia Drugs 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- CJHJAADHCLSWGJ-UHFFFAOYSA-N methyl 7-fluoro-6-methyl-1-benzothiophene-2-carboxylate Chemical compound FC1=C(C=CC2=C1SC(=C2)C(=O)OC)C CJHJAADHCLSWGJ-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UVEWQKMPXAHFST-UHFFFAOYSA-N n,1-diphenylmethanimine Chemical class C=1C=CC=CC=1C=NC1=CC=CC=C1 UVEWQKMPXAHFST-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000001608 tolans Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D333/56—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
Definitions
- the present invention relates to 2,3-dihydrobenzothiophene derivatives, to the use thereof in liquid-crystalline or mesogenic media, to liquid-crystalline or mesogenic media comprising these derivatives, and to electro-optical display elements containing these liquid-crystalline or mesogenic media.
- Liquid crystals have found widespread use since the first commercially usable liquid-crystalline compounds were found about 30 years ago.
- Known areas of application are, in particular, displays for watches and pocket calculators, and large display panels as used in railway stations, airports and sports arenas. Further areas of application are displays of portable computers and navigation systems and video applications. For the last-mentioned applications in particular, high demands are made of the response times and contrast of the images.
- the spatial arrangement of the molecules in a liquid crystal has the effect that many of its properties are direction-dependent.
- optical, dielectric and elastomechanical anisotropies are the optical, dielectric and elastomechanical anisotropies.
- the dielectric constant ⁇ of the liquid-crystalline medium has different values for the two orientations.
- Substances whose dielectric constant is larger when the longitudinal axes of the molecules are oriented perpendicular to the capacitor plates than when they are oriented parallel are known as being dielectrically positive.
- Most liquid crystals used in conventional displays fall into this group.
- the dipole moment oriented along the longitudinal axis of the molecules is larger than the dipole moment oriented perpendicular to the longitudinal axis of the molecules.
- the orientation of the larger dipole moment along the longitudinal axis of the molecule also determines the orientation of the molecule in a liquid-crystal display in the field-free state.
- TN twisted nematic
- a liquid-crystalline layer with a thickness of only from about 5 to 10 ⁇ m is arranged between two flat glass plates, onto each of which an electrically conductive, transparent layer of tin oxide or indium tin oxide has been vapour-deposited as electrode.
- a likewise transparent alignment layer is located between these films and the liquid-crystalline layer.
- This alignment layer serves to bring the longitudinal axes of the adjacent crystalline molecules into a preferential direction through surface forces in such a way that, in the voltage-free state, they lie uniformly on the inside of the display surface with the same alignment in a flat manner or with the same small tilt angle.
- Two polarisation films which only enable linear-polarised light to enter and escape are adhesively bonded to the outside of the display in a certain arrangement.
- IPS in-plane switching
- FFS farnesoid-field switching
- FFS displays have a low viewing-angle dependence of the contrast.
- FFS displays usually contain an LC medium with positive dielectric anisotropy, and an alignment layer, usually of polyimide, which provides planar alignment to the molecules of the LC medium.
- An object of the present invention was to provide compounds having advantageous properties for use in liquid-crystalline media.
- a further object of the present invention is to provide liquid-crystalline media, in particular for use in VA, IPS or FFS displays.
- the compounds of formula I are seleced from compounds of the sub-formula Ia wherein the occurring groups and parameters have the meanings given above and is selected from the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, and decaline-2,6-diyl, in which one or more non-adjacent CH 2 groups may be replaced by -O- and/or -S- and in which one or more H atoms may be replaced by F, and preferably has the meaning given for and independently of one another, are selected from the group consisting of 1,4-phenylene and 2,6-naphthylene, in which one or two CH groups may be replaced by N and in which, in addition, one or more H atoms may be replaced by F, Cl, or CF 3 , and m, p and q independently of one another, are 0 or 1.
- Preferred compounds of formula Ia are selected from the following sub-formulae: wherein R 11 , R 21 , R 22 , Y, A 21 and A 22 have the meanings indicated above and preferably
- the compounds of formula I are seleced from compounds of the sub-formula Ib wherein the occurring groups and parameters have the meanings given above for formula I, and is selected from the group consisting of 1,4-phenylene and 2,6-naphthylene, in which one or two CH groups may be replaced by N and in which, in addition, one or more H atoms may be replaced by F, Cl or CF 3 , and preferably has the meaning given for and alternatively is selected from the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, and decaline-2,6-diyl, in which one or more non-adjacent CH 2 groups may be replaced by -O- and/or -S- and in which one or more H atoms may be replaced by F, and independently of one another, have the meaning given for and m, p and q independently of one another, are 0 or 1.
- Preferred compounds of formula Ib are wherein R 11 , R 21 , R 22 , Y, A 21 and A 22 have the meanings indicated above and preferably
- the compounds according to the invention all have negative ⁇ and are therefore suitable, in particular, for use in VA-TFT displays, and in IPS- and FFS displays.
- the compounds according to the invention preferably have a ⁇ of ⁇ -2.5, more preferably of ⁇ -5 and particularly preferably a ⁇ of ⁇ -8. They exhibit very good compatibility with the conventional substances used in liquid-crystal mixtures for displays.
- trans-1,4-cyclohexylene denote 1,4-phenylene.
- R 11 , R 21 , R 22 and L are an alkyl radical and/or an alkoxy radical, this can be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6 or 7 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.
- R 11 , R 21 , R 22 and L may each, independently of one another, be an alkenyl radical having from 2 to 15 carbon atoms, which may be straight-chain or branched. It is preferably straight-chain and has from 2 to 7 carbon atoms. Accordingly, it is preferably vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, or hept-1-, -2-, -3-, -4-, -5- or -6-enyl.
- R 11 , R 21 , R 22 and L may each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms in which one CH 2 group has been replaced by -O- and one has been replaced by -CO-, where these are preferably adjacent. This thus contains an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-. This is preferably straight-chain and has from 2 to 6 carbon atoms.
- R 11 , R 21 , R 22 and L may each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms or alkenyl radical having from 2 to 15 carbon atoms, each of which is monosubstituted by -CN or -CF 3 and is preferably straight-chain. The substitution by -CN or -CF 3 is possible in any desired position.
- R 11 , R 21 , R 22 and L may each, independently of one another, be an alkyl radical in which two or more CH 2 groups have been replaced by -O- and/or -CO-O-, where this may be straight-chain or branched. It is preferably branched and has from 3 to 12 carbon atoms.
- R, L 2 , L 3 , L 4 and L 6 may each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms or an alkenyl radical having from 2 to 15 carbon atoms, each of which is at least monosubstituted by halogen, where these radicals are preferably straight-chain and halogen is preferably -F or -CI. In the case of polysubstitution, halogen is preferably -F.
- the resultant radicals also include perfluorinated radicals, such as -CF 3 . In the case of monosubstitution, the fluorine or chlorine substituent can be in any desired position, but is preferably in the ⁇ -position.
- the compounds of the general formula I are prepared by methods known per se, as described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and are suitable for the said reactions. Use can be made here of variants which are known per se, but are not mentioned here in greater detail.
- the starting materials can also be formed in situ by not isolating them from the reaction mixture, but instead immediately converting them further into the compounds of the general formula I
- the compounds of formula I are preferably synthesized as shown in schemes 1 and 2.
- Aldehydes 2 are synthesised by orthometallation of fluorobenzenes (1) followed by formylation with e.g. N-formylpiperidine.
- Knoevenagel condensation with methyl mercaptoacetate and intramolecular nucleophiolic replacement of fluoride yields benzothiophene carboxylic acid esters 3 which can be saponified to give carboxylic acids 4.
- the latter undergo decarboxylation when heated in quinoline in the presence of copper.
- the resulting benzothiophene (5) can be metallated with butyllithium to give key intermediate 6.
- Key intermediate 6 is further transferred into derivatives according to the invention by a variety of reactions, e.g. addition to carbonyl compounds or transition metal catalysed cross coupling reactions with aromatic halides.
- Such a transformation is exemplified by the reaction with a cyclohexanone derivative (7) to give alcohols 8, which can be dehydrated and hydrogenated to give benzothiophenes 9 (scheme 2).
- the double bond in the thiophene ring is not hydrogenated in this synthetic step.
- This reaction is performed in a last step of the synthesis to give diydrobenzothiophenes 10.
- Another object of the present invention is a process of the preparation of a compound of formula I by hydrogenation of a compound of formula II in which the occurring groups and parameters have the meanings indicated above for formula I.
- the compounds of the general formula I can be used in liquid-crystalline media.
- the present invention therefore also relates to a liquid-crystalline medium comprising two or more liquid-crystalline compounds, comprising one or more compounds of the general formula I.
- the present invention also relates to liquid-crystalline media comprising from 2 to 40, preferably from 4 to 30, components as further constituents besides one or more compounds of the formula I according to the invention. These media particularly preferably comprise from 7 to 25 components besides one or more compounds according to the invention.
- nematic or nematogenic (monotropic or isotropic) substances are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of the azoxy-benzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl esters of cyclohexanecarboxylic acid, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoic acid, of cyclohexanecarboxylic acid or of cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, cycl
- L and E which may be identical or different, are each, independently of one another, a divalent radical from the group formed by -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- and their mirror images, where Phe is unsubstituted or fluorine-substituted 1,4-phenylene, Cyc is trans-1,4-cyclohexylene or 1,4-cyclohexenylene, Pyr is pyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio is 1,3-dioxane-2,5-diyl, and G is 2-(trans-1,4-cyclohexyl)ethyl.
- One of the radicals L and E is preferably Cyc or Phe. E is preferably Cyc, Phe or Phe-Cyc.
- the media according to the invention preferably comprise one or more components selected from the compounds of the formulae (1), (2), (3), (4) and (5) in which L and E are selected from the group consisting of Cyc and Phe and simultaneously one or more components selected from the compounds of the formulae (1), (2), (3), (4) and (5) in which one of the radicals L and E is selected from the group consisting of Cyc and Phe and the other radical is selected from the group consisting of -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulae (1), (2), (3), (4) and (5) in which the radicals L and E are selected from the group consisting of -Phe-Cyc-, -Cyc-Cyc
- R' and R" are each, independently of one another, alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 carbon atoms.
- This smaller sub-group is called group A below, and the compounds are referred to by the sub-formulae (1a), (2a), (3a), (4a) and (5a).
- R' and R" are different from one another, one of these radicals usually being alkyl, alkenyl, alkoxy or alkoxyalkyl.
- R' and R" are as defined for the compounds of the sub-formulae (1a) to (5a) and are preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.
- R" is -CN.
- This sub-group is referred to below as group C, and the compounds of this sub-group are correspondingly described by sub-formulae (1c), (2c), (3c), (4c) and (5c).
- R' is as defined for the compounds of the sub-formulae (1a) to (5a) and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.
- the media according to the invention preferably comprise one or more compounds selected from groups A, B and/or C.
- the proportions by weight of the compounds from these groups in the media according to the invention are: group A: from 0 to 90%, preferably from 20 to 90%, in particular from 30 to 90% group B: from 0 to 80%, preferably from 10 to 80%, in particular from 10 to 70% group C: from 0 to 80%, preferably from 5 to 80%, in particular from 5 to 50%.
- the media according to the invention preferably comprise from 1 to 40%, particularly preferably from 5 to 30%, of the compounds of the formula I according to the invention. Preference is furthermore given to media comprising more than 40%, in particular from 45 to 90%, of compounds of the formulae formula I according to the invention.
- the media preferably comprise three, four or five compounds of the formula I according to the invention.
- the media according to the invention are prepared in a manner conventional per se.
- the components are dissolved in one another, advantageously at elevated temperature.
- the liquid-crystalline phases of the present invention can be modified in such a way that they can be used in all types of liquid-crystal display elements that have been disclosed hitherto.
- Additives of this type are known to the person skilled in the art and are described in detail in the literature ( H. Kelker/R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Wein-heim, 1980 ).
- pleochroic dyes can be used for the preparation of coloured guest-host systems or substances can be added in order to modify the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases.
- the present invention also relates to electro-optical liquid-crystal display elements containing a liquid-crystalline medium according to the invention.
- ⁇ n denotes the optical anisotropy (589 nm, 20°C) and ⁇ denotes the dielectric anisotropy (1 kHz, 20°C).
- ⁇ and ⁇ n values of the compounds according to the invention are obtained by extrapolation from liquid-crystalline mixtures consisting of 10% of the respective compound according to the invention and 90% of the commercially available liquid-crystal mixture ZLI-2857 (for ⁇ ) or ZLI-4792 (for ⁇ n) (Merck KGaA, Darmstadt). In cases of limited solubility, the compound is measured in a mixture comprising only 5% of the compound, which is noted by the addition (5%) after the values in question.
- a solution of BuLi (15% in hexane, 140 mL, 0.219 mol) is added dropwise to a stirred solution of 1-butoxy-2,3-difluorobenzene (40.0 g, 0.215 mol) in THF (160 mL) at -70 °C.
- the mixture is stirred for 30 min at the same temperature before it is treated with a solution of N-formylpiperidine (24.5 mL, 0.221 mol) in THF (80 mL).
- the reaction mixture is allowed to warm to -30°C, treated with water and conc. HCl (until pH 6).
- the aqueous phase is separated and extracted with MTB ether (2 times).
- a solution of BuLi (15% in hexane, 30.8 mL, 49.0 mmol) is added dropwise to a solution of 6-butoxy-7-fluoro-benzothiophene (10.0 g, 44.5 mmol) in THF (40 mL) at -70 °C.
- the mixture is stirred for 1 h at the same temperature before a solution of 4-propylcyclohexanone (7.5 g, 53.5 mmol) in THF (10 mL) is added.
- the reaction mixture is stirred for 1 hat -70 °C before it is allowed to warm to room temperature, quenched with sat. ammonium chloride solution, extracted with MTB ether, dried over Na 2 SO 4 , filtered and concentrated under reduced pressure.
- reaction mixture is concentrated under reduced pressure and purified by flash chromatography (heptane/chlorobutane), followed by recrystallization from heptane to give 6-butoxy-7-fluoro-2-(4-propylcyclohexyl)-2,3-dihydrobenzothiophene as colourless crystals.
- the compounds are distinguished by a high negative dielectric anisotropy and high clearing temperatures which makes them very suitable for applications in liquid crystalline media for VA, IPS and FFS displays.
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
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Claims (12)
- Composé de la formule IR11, R21 et R22 représentent chacun, de manière identique ou différente, F, Cl, Br, I, CN, SCN, OH, SF5, alkyle en chaîne droite ou ramifié qui comporte jusqu'à 15 atomes de C, lequel peut être non substitué, mono- ou polysubstitué par F, Cl, Br, I ou CN étant entendu qu'il est également possible qu'un ou plusieurs groupe(s) CH2 non adjacents soit/soient remplacé(s), dans chaque cas de manière indépendante les uns des autres, parA11, A12 A21 et A22 représentent chacun, de manière indépendante les uns des autres, un radical qui est sélectionné parmi les groupes qui suivent :a) le groupe qui est constitué par trans-1,4-cyclohexylène, 1,4-cyclohexénylène, et décaline-2,6-diyle, où un ou plusieurs groupe(s) CH2 non adjacents peut/peuvent être remplacé(s) par -O- et/ou par -S- et où un ou plusieurs atome(s) de H peut/ peuvent être remplacé(s) par F,b) le groupe qui est constitué par 1,4-phénylène et 2,6-naphtylène, où un ou deux groupe(s) CH peut/peuvent être remplacé(s) par N et où, en outre, un ou plusieurs atome(s) de H peut/peuvent être remplacé(s) par L,c) le groupe qui est constitué par 1,3-dioxane-2,5-diyle, tétrahydrofuran-2,5-diyle, cyclobutane-1,3-diyle, thiophène-2,5-diyle, sélénophène-2,5-diyle et 1,2,3,4-tétrahydronanaphtaline-2,6-diyle, dont chacun peut être mono- ou polysubstitué par L,d) le groupe qui est constitué par bicyclo[1.1.1]pentane-1,3-diyle, bicyclo[2.2.2]octane-1,4-diyle, et spiro[3.3]heptane-2,6-diyle, où un ou plusieurs atome(s) de H peut/peuvent être remplacé(s) par FL représentent chacun, de manière identique ou différente, un groupe halogène, cyano, alkyle, alcoxy, alkylcarbonyle ou alcoxycarbonyle qui comporte de 1 à 7 atome(s) de C, où un ou plusieurs atome(s) de H peut/peuvent être substitué(s) par F ou par Cl,Z11 et Z12 représentent, de manière indépendante l'un de l'autre, une liaison simple, -CF2O-, -OCF2-, -CH2CH2-, -CF2CF2-, -C(O)O-, -OC(O)-, -CH2O-, -OCH2-, -CF=CH-, -CH=CF-, -CF=CF-, -CH=CH- ou -C≡C-, de préférence -CH2CH2-, -CF2CF2-, -CH=CH- ou une liaison simple,Y représente H, F, Cl, CF3, ou OCF3, de préférence F,m et n sont, de manière indépendante l'un de l'autre, 0, 1 ou 2, étant entendu qu'au moins l'un de m et n représente 0.
- Composé de la formule I selon la revendication 1, dans lequel le composé est sélectionné parmi les composés de la sous-formule la
- Composé de la formule I selon la revendication 1, dans lequel le composé est sélectionné parmi les composés de la sous-formule Ib
- Composé de la formule I selon une ou plusieurs des revendications 1 à 3, dans lequel Z11 et Z12 représentent une liaison simple.
- Composé de la formule I selon une ou plusieurs des revendications 1 à 6 dans lequel
- Composé selon une ou plusieurs des revendications 1 à 7, dans lequelR11 représente alkyle, alkényle ou alcoxy qui comporte jusqu'à 7 atomes de C, où un ou plusieurs atome(s) de H peut/peuvent être remplacé(s) par fluor, etR21 et R22 représentent, de manière indépendante l'un de l'autre, alkyle, alkényle ou alcoxy qui comporte jusqu'à 7 atomes de F, Cl, CN, SCN, SF5, CF3, OCF3, OCF2H, OCHF2, ou -OCH=CF2.
- Procédé pour la préparation de composés de la formule I selon la revendication 1, caractérisé en ce qu'un composé de la formule II
est hydrogéné en présence d'un catalyseur. - Utilisation d'un composé selon une ou plusieurs des revendications 1 à 8 dans les milieux cristallins liquides.
- Milieu cristallin liquide comprenant deux composés cristallins liquides ou plus, caractérisé en ce qu'il comprend un ou plusieurs composé(s) selon une ou plusieurs des revendications 1 à 8.
- Élément d'affichage électrooptique contenant un milieu cristallin liquide selon la revendication 11.
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EP17178476 | 2017-06-28 | ||
PCT/EP2018/066935 WO2019002196A1 (fr) | 2017-06-28 | 2018-06-25 | Dérives du 2,3-dihydrobenzothiophène |
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EP3645662A1 EP3645662A1 (fr) | 2020-05-06 |
EP3645662B1 true EP3645662B1 (fr) | 2021-03-24 |
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EP18732360.5A Active EP3645662B1 (fr) | 2017-06-28 | 2018-06-25 | Dérives du 2,3-dihydrobenzothiophène |
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US (1) | US11174432B2 (fr) |
EP (1) | EP3645662B1 (fr) |
KR (1) | KR20200024242A (fr) |
CN (1) | CN110799627B (fr) |
TW (1) | TWI772448B (fr) |
WO (1) | WO2019002196A1 (fr) |
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WO2019002196A1 (fr) * | 2017-06-28 | 2019-01-03 | Merck Patent Gmbh | Dérives du 2,3-dihydrobenzothiophène |
CN116948657A (zh) * | 2023-06-28 | 2023-10-27 | 北京燕化集联光电技术有限公司 | 液晶化合物、组合物及其应用 |
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US4816473A (en) * | 1983-07-14 | 1989-03-28 | Syntex (U.S.A.) Inc. | Aroyl benzofuran and benzothiophene acetic and propionic acids |
JPS61158976A (ja) * | 1984-12-28 | 1986-07-18 | Shionogi & Co Ltd | ベンゾフランおよびベンゾチオフエン誘導体 |
DE102004053279A1 (de) | 2003-11-25 | 2005-06-23 | Merck Patent Gmbh | Benzofuran- und Benzothiophen-Derivate, Verfahren zu ihrer Herstellung sowie ihre Verwendung |
WO2015101928A1 (fr) | 2013-12-31 | 2015-07-09 | Aurigene Discovery Technologies Limited | Dérivés de thiophène et de thiazole fusionnés utilisés en tant que modulateurs gamma ror |
DE102016003902A1 (de) * | 2015-04-13 | 2016-10-13 | Merck Patent Gmbh | Fluorierte Dibenzofuran- und Dibenzothiophenderivate |
WO2019002196A1 (fr) * | 2017-06-28 | 2019-01-03 | Merck Patent Gmbh | Dérives du 2,3-dihydrobenzothiophène |
-
2018
- 2018-06-25 WO PCT/EP2018/066935 patent/WO2019002196A1/fr unknown
- 2018-06-25 US US16/627,056 patent/US11174432B2/en active Active
- 2018-06-25 EP EP18732360.5A patent/EP3645662B1/fr active Active
- 2018-06-25 KR KR1020207001934A patent/KR20200024242A/ko not_active Application Discontinuation
- 2018-06-25 CN CN201880043586.6A patent/CN110799627B/zh active Active
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Also Published As
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CN110799627B (zh) | 2023-07-07 |
KR20200024242A (ko) | 2020-03-06 |
EP3645662A1 (fr) | 2020-05-06 |
US20200123444A1 (en) | 2020-04-23 |
TWI772448B (zh) | 2022-08-01 |
TW201904953A (zh) | 2019-02-01 |
WO2019002196A1 (fr) | 2019-01-03 |
CN110799627A (zh) | 2020-02-14 |
US11174432B2 (en) | 2021-11-16 |
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